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Synthesis of Zirconium Based Metal-Organic Frameworks with Novel Topology and Post-synthetic Functionalization
Metal-organic frameworks (MOFs) is a class of porous crystalline material that have shown good performance in various applications such as gas storage, separation, catalysis, sensing due to their permanent porosity and tunable functionalities. As an emerging subgroup of MOFs, Zr-MOFs have drawn great attention due to their excellent chemical stability and rich chemistry through cluster modification. ^ In this dissertation, Zr-MOFs are constructed with a series of tetracarboxylic ligands with tetrahedral, planar, and bent geometry. We have discovered NPF-200 with the novel 4,12,12T1 topology which is the first example among all MOFs. NPF-200 has been successfully activated with a BET surface area of 5463 m 2 g-1. Isostructural MOF NPF-201 encapsulates cationic photocatalyst Ru(bpy)32+ and catalyzes thioanisole photo-oxidation reaction. Multivariant MOFs (MTV-MOFs) have been constructed through post-synthetic secondary ligand insertion strategy with NPF-300. Porosity and gas adsorption have been improved significantly after ligand insertion. We further explore the MTV-MOFs for photocatalysis by insertion photosensitizer and transition metal catalyst in mesoporous NPF-400. We have also discovered a rare interpenetrated scu topology for post-synthetic metalation and two-dimensional carbazolic Zr-MOFs.^
Zhang, Xin, "Synthesis of Zirconium Based Metal-Organic Frameworks with Novel Topology and Post-synthetic Functionalization" (2018). ETD collection for University of Nebraska - Lincoln. AAI10842989.